Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
  • C08G64/0208—Aliphatic polycarbonates saturated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
  • C08L2666/18—Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof

Definitions

• the present invention relates to a polycarbonate resin composition having a high Abbe's number and high strength and excellent stainability.
• BPA 2,2-bis(4-hydroxyphenyl)propane
• the bisphenol resins formed of only BPA have a large photoelastic coefficient, and the molded articles formed of the resins may have large birefringence due to the relatively inferior melt-flowability thereof.
• the resins have a high refractive index, 1.58, but they have a low Abbe's number, 30, which indicates that the refractive index and the Abbe's number are ill-balance. Therefore, they suffer from the disadvantage of not having capabilities sufficient for being used in a variety of the applications such as optical recording materials and optical lenses. Furthermore, they suffer from the disadvantages of having the low stainability and of forming only the lenses of the limited color
• An object of the invention is to provide a polycarbonate resin composition having a high refractive index, high Abbe's number, high strength, excellent hue and excellent stainability.
• the present inventors conducted studies in order to solve the above-described problems, as a result, found that it was possible to obtain a transparent polycarbonate resin composition having high refractive index, high Abbe's number, high strength, excellent hue and excellent stainability by blending a polycarbonate resin derived from a predetermined dihydroxy compound and a polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane, and then made the present invention.
• the present invention relates to a polycarbonate resin composition prepared by blending
• a polycarbonate resin (A) prepared by forming carbonate bonds in tricyclo[5.2.1.0 2,6 ]decanedimethanol, represented by formula (1), with a diester or phosgene, and a weight-averaged molecular weight (Mw) of the polycarbonate resin (A) being equal to or more than 25,000, and
• a polycarbonate resin (B) prepared by reacting 2,2-bis(4-hydroxyphenyl)propane, represented by formula (2), and phosgene, and weight-averaged molecular weight (Mw) of the polycarbonate resin (B) being equal to or more than 30,000, wherein
• a ratio thereof, 100 ⁇ (A)/((A)+(B)), is from 1 to 99% by weight.
• the polycarbonate resin composition of the present invention has the well-balanced refractive index and the Abbe's number, has a high strength and excellent hue and stainability, and may be used as a variety of optical materials such as eyeglass lenses, in-car lenses, covers, windowpanes and touch panels.
• the polycarbonate (A), which is an ingredient of the blended composition of the invention, may be obtained by carrying out the polymerization of TCDDM in a presence of a diester carbonate and catalyst according to any known melt-polycondensation method. It may be prepared also according to a method in which the reaction with phosgene is carried out.
• the polycarbonate resin (B) may be obtained by polymerization of BPA according to a known phosgene method (interfacial polymerization method).
• the blend ratio by weight of the polycarbonate resins (A) and (B), 100 ⁇ (A)/((A)+(B)), is from 1 to 99% by weight.
• the ratio is from 3 to 70% by weight, or more preferably, from 5 to 60% by weight.
• the composition having the blend ratio of smaller than 1% by weight has the low Abbe's number and no stainability, which is not preferable.
• the composition having the blend ratio of more than 99% by weight has the low heat resistance, low impact strength and furthermore the low refractive ratio, which is not preferable.
• the polystyrene-converted weight average molecular weight (Mw) of the polycarbonate resin (A) is equal to or more than 25,000, preferably from 25,000 to 300,000, more preferably from 35,000 to 150,000, or even more preferably from 35,000 to 100,000.
• the blended resin composition containing the polycarbonate resin (A) whose Mw is smaller than 25,000 may be brittle, which is not preferable.
• the polycarbonate resin composition containing the polycarbonate resin (A) whose Mw is more than 300,000 has a high melt viscosity, which may require undesirable severer conditions for being blended. Furthermore, such a resin composition may be subjected to an injection molding under severer conditions, which may cause undesirable silver patterns in the molded products.
• the polystyrene-converted weight average molecular weight (Mw) of the polycarbonate resin (B) is equal to or more than 30,000, preferably from 30,000 to 250,000, more preferably from 30,000 to 110,000, or even more preferably from 30,000 to 100,000.
• the blended resin composition containing the polycarbonate resin (B) whose Mw is smaller than 30,000 may be brittle, which is not preferable.
• the polycarbonate resin composition containing the polycarbonate resin (B) whose Mw is more than 250,000 has a high melt viscosity, which may require severer conditions for being blended. Furthermore, such a resin composition may be subjected to an injection molding under severer conditions, which may cause undesirable silver patterns in the molded products.
• the difference ( ⁇ Mw) of polystyrene-converted weight average molecular weight (Mw) between the polycarbonate resins (A) and (B) is preferably from 0 to 120,000, more preferably from 0 to 80,000, or even more preferably from 0 to 50,000.
• the polycarbonate resins (A) and (B), whose ⁇ Mw is more than 120,000, may show a remarkably large difference in viscosity therebetween, and may be compatible hardly. Therefore, the resin composition, containing such the polycarbonate resins, may show lowered transparency, which is not preferable.
• the glass-transition temperature (Tg) of the blended resin composition of the invention is preferably from 95 to 180 degrees Celsius, or more preferably from 105 to 170 degrees Celsius.
• the composition, having Tg of lower than 95 degrees Celsius may be used in only a narrow temperature range, which is not preferable.
• the composition, having Tg of higher than 180 degrees Celsius may have to be subjected to a molded process under severer conditions, which is not preferable.
• the method for preparing the polycarbonate resin (A) is not limited, and the polycarbonate resin (A) may be prepared according to any method in which carbonate bonds are formed in the diol compound represented by the above-described formula (1) with a diester or phosgene.
• the method for preparing the polycarbonate resin (A) the known melt-polycondensation method, in which the reaction of the diol compound represented by the above-described formula (1) and a diester-carbonate is carried out in presence of a basic-compound catalyst, transesterification catalyst or mixed catalyst thereof, is preferably used.
• diphenyl carbonate ditolyl carbonate, bis(chlorophenyl)carbonate, m-crezyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like are exemplified.
• diphenyl carbonate is especially preferable.
• Diphenyl carbonate is preferably used by a ratio of from 0.90 to 1.15 moles, or more preferably by a ratio of from 0.95 to 1.05 moles, with respect to 1 mole of the total of the dihydroxy compounds.
• alkali metal and/or alkali earth metal compounds, nitrogen-containing compounds and the like are especially exemplified.
• Specific examples thereof include organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides, and alkoxides of alkali metal and alkali earth metal compounds; and quaternary ammonium hydroxides and the salts thereof, and amines. They may be used alone respectively or in combination thereof.
• magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate or the like are used.
• quaternary ammonium hydroxides having an alkyl or aryl group such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide and trimethylbenzyl ammonium hydroxide; tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as propylamine and butylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzimidazole; bases and basic salts such as ammonia, tetramethyl ammonium borohydride, tetrabutyl ammonium borohydride, tetrabutyl ammonium tetraphenylborate, tetraphen
• salts of zinc, tin, zirconium or lead are preferably used, and may be used alone respectively or in combination thereof.
• These catalysts may be respectively used preferably by a ratio of from 10 ⁇ 9 to 10 ⁇ 3 mole, or more preferably by a ratio of from 10 ⁇ 7 to 10 ⁇ 4 mole, with respect to 1 mole of the total dihydroxy compounds.
• the above-described raw materials and catalyst are used, and the melt-polycondensation is carried out by interesterification reaction thereof under heat and under an ordinary or reduced pressure while the by-products are removed.
• the reaction is usually carried out in two or more multiple-stage step.
• the reaction in the first stage is carried out at a temperature of from 120 to 220 degrees Celsius, or preferably at a temperature of from 160 to 200 degrees Celsius, under a pressure of from an ordinary pressure to 200 Torr for from 0.1 to 5 hours, or preferably for from 0.5 to 3 hours.
• the reaction is continuously carried out while the temperature is gradually raised to a final temperature of from 230 to 260 degrees Celsius and the pressure is gradually reduced to a final pressure of equal to or less than 1 Torr.
• the polycondensation is carried out at a temperature of from 230 to 260 degrees Celsius under a reduced pressure of not more than 1 Torr, and then, is terminated by recovering pressure with nitrogen gas when the viscosity reaches the desired value.
• the reaction time under a pressure of not more than 1 Torr is from 0.1 to 2 hours, the total reaction time is from 1 to 6 hours, or usually from 2 to 5 hours.
• reaction device to be used may be any vertical type equipped with an anchor agitating blade, maxblend agitating blade, helical ribbon agitating blade or the like, any horizontal type equipped with a paddle agitating blade, grid agitating blade, glass agitating blade or the like, or any extruder type equipped with a screw. And they may be used in combination considering the viscosity of the polymerized
• the catalyst is removed or deactivated in order to maintain heat stability and hydrolysis stability of the polycarbonate resin thus obtained.
• a method for deactivating a catalyst by addition of known acid substance is suitably applied.
• the acid substance include aromatic sulfonic acids such as p-toluene sulfonic acid, aromatic sulfonic acid esters such as butyl p-toluene-sulfonate and hexyl p-toluenesulfonate, aromatic sulfonic acid salts such as dodecylbenzene sulfonic acid tetrabutyl phosphonium salt, organic halides such as stearoyl chloride, benzoyl chloride and p-toluene-sulfonyl chloride, alkyl sulfates such as dimethyl sulfate and organic halides such as benzyl chloride.
• a step to remove low boiling point compounds in the polymer with vaporization under a pressure of 0.1 to 1 Torr at a temperature of from 200 to 350 degrees Celsius may be added.
• a horizontal apparatus equipped with a stirring blade with excellent surface renewing capacity such as paddle blade, lattice blade, spectacle shaped blade, etc. or thin film vaporizer is suitably used.
• an antioxidant, pigment, dyestuff, reinforcing agent, filler, ultraviolet absorber, lubricating agent, releasing agent, crystalline nucleus agent, plasticizer, flowability improving agent, antistatic agent, antibacterial agent or the like is preferably added along with the heat resistance agent or the hydrolytic stability agent.
• the polycarbonate resin (B) can be obtained by polymerization of the hydroxy compound represented by the above-described formula (2) according to the known phosgene method (interfacial polymerization method).
• the polycarbonate resin (B) can be prepared according to the interfacial polymerization method in which the dihydroxy compound represented by the above-described formula (2) is reacted with phosgene in a presence of solvent, an end-stopping agent and an acid-binding agent.
• the dihydroxy compound and the end-stopping agent are dissolved in an aqueous solution of the acid-binding agent, and the reaction is carried out in a presence of organic solvent.
• the acid-binding agent for example, pyridine, or hydroxides of alkali metal such as sodium hydroxide and potassium hydroxide are preferably used.
• the solvent for example, methylene chloride, chloroform, chlorobenzene, xylene or the like is preferably used.
• tertiary amines such as triethyl amine, or quaternary ammonium salts such as tetra-n-butyl ammonium bromide are used.
• end-stopping agent which is used for adjusting the polymerization degree
• mono-functional hydroxy compounds such as phenol, p-tert-butylphenol, p-cumylphenol and phenols having a long alkyl group are used.
• an antioxidant such as sodium sulfite and sodium hydrosulfite may be added.
• the reaction is usually carried out at a temperature of from 0 to 150 degrees Celsius, or preferably at a temperature of from 5 to 40 degrees Celsius.
• the reaction time depends on the reaction temperature, and, the reaction time is usually from 0.5 min. to 10 hours, or preferably from 1 min. to 2 hours.
• the pH value of the reaction system is kept equal to or more than 10 during the reaction.
• the blended resin composition of the present invention may be prepared according to the method in which solids of polycarbonate resins (A) and (B) are prepared respectively, blended and then kneaded by a kneading machine, the method in which a solid of the polycarbonate resin (B) is added to the polycarbonate resin (A) in a molten state, or a solid of the polycarbonate resin (A) is added to the polycarbonate resin (B) in a molten state and then kneaded by a kneading machine.
• the blended resin composition of the present invention may be prepared according to the method in which polycarbonate resins (A) and (B) are blended in a molten state and then kneaded by a kneading machine. Kneading may be performed in a continuous process or in a batch wise. As the kneading machine, any of an extruder, labopastomill and kneader may be used. When kneading is performed in a batch wise, a labopastomill or a kneader is suitably applied. When any polycarbonate resin produced by a melt-polycondensation process is used, it is preferable to perform kneading after deactivation of a catalyst in terms of avoiding transesterfication during kneading.
• a process for producing the polycarbonate resin composition of the present invention also a process comprising dissolving the polycarbonate resins (A) and (B) in a solvent and pouring it into a mold and then vaporizing the solvent may be applied.
• the solvent methylene chloride, chloroform and cresol are used. According to the process, it is possible to dissolve and add any additive at the same time, which is convenient.
• antioxidant a releasing agent, an ultraviolet absorber, a flowability improving agent, a reinforcing agent, crystalline nucleus agent, dyestuff, an antistatic agent, and an antibacterial agent may be added to the blended resin composition of the present invention.
• additives may be added to each the resins (A) and (B) or either one thereof prior to blending and kneading or may be added and kneaded at the same time during blending and kneading or may be kneaded after blending.
• the obtained pellets were pressured into circular-disk shapes of a 50 mm-diameter and a 3 mm-thickness.
• the circular disk was transparent.
• the YI value of the circular disk was 1.68, which indicated that the coloration was remarkably low.
• the result of the falling-ball test was equal to or more than 535 g, which indicated the high impact strength.
• the result of the stainability test was 91%, which indicated high stainability.
• the obtained pellets were pressured into circular-disk shapes of a 50 mm-diameter and a 3 mm-thickness.
• the circular disk was transparent.
• the YI value of the circular disk was 1.77, which indicated that the coloration was significantly low.
• the result of the falling-ball test was equal to or more than 535 g, which indicated the high impact strength.
• the result of the stainability test was 88%, which indicated high stainability.
• the obtained pellets were pressured into circular-disk shapes of a 50 mm-diameter and a 3 mm-thickness.
• the circular disk was transparent.
• the physical properties of the obtained resin were summarized in Table 1.
• the YI value of the circular disk was 1.69, which indicated that the coloration was remarkably low.
• the result of the falling-ball test was equal to or more than 535 g, which indicated the high impact strength.
• the result of the stainability test was 80%, which indicated high stainability.
• the pellets of a polycarbonate resin “Iupilon S-3000” (manufactured by Mitsubishi Engineering-Plastics Corporation), were pressured into circular-disk shapes of a 50 mm-diameter and a 3 mm-thickness. The measurements of the physical properties and the tests were carried out, and the results are summarized in Table 1. The Abbe's number thereof was low, 30; and the stainability thereof was very low, 8%.
• the pellets of the polycarbonate (A) were pressured into circular-disk shapes of a 50 mm-diameter and a 3 mm-thickness.
• the measurements of the physical properties and the tests were carried out, and the results are summarized in Table 1.
• the refractive index thereof was low, 1.527; and the Tg thereof was very low, 80 degrees Celsius.
• the impact strength thereof was low, 16 g.
• the temperature was raised to 240 degrees Celsius at 37.5 degrees Celsius/hr, and then maintained at 240 degrees Celsius for at 150 Torr 10 minutes. After that, the pressure was reduced to 120 Torr for 10 minutes, and then maintained at 240 degrees Celsius at 120 Torr for 70 minutes. After that, the pressure was reduced to 100 Torr for 10 minutes, and then maintained at 240 degrees Celsius at 100 Torr for 10 minutes. The pressure was reduced to 1 Torr or less for 40 minutes, and then the polymerization was carried out at 240 degrees Celsius at a pressure of equal to or less than 1 Torr for 10 minutes under stirring. After termination of the reaction, nitrogen gas was blown into the vessel for pressurizing, and then the produced polycarbonate resin was taken out while being subjected to pelletization. Polycarbonate resin (X) having MFR of 10.0 g/10 min and Tg of 108 degrees Celsius was obtained.
• the obtained pellets of the polycarbonate resin (X) were pressured into circular-disk shapes of a 50 mm-diameter and a 3 mm-thickness.
• the measurements of the physical properties and the tests were carried out, and the results were summarized in Table 1.
• the impact strength was low, 16 g; the YI value was 3.15, which indicated that coloration thereof was remarkable.
• the obtained pellets were pressured into circular-disk shapes of a 50 mm-diameter and a 3 mm-thickness.
• the circular disk was transparent.
• the measurements of the physical properties and the tests were carried out, and the results were summarized in Table 1.
• the impact strength was slightly low, 150 g; and the YI value was 2.83, which indicated that coloration was recognized.
• Example 1 Refractive Abbe's Index Number Tg Stainability Strength YI
• Example 2 1.567 35 125 88 >535 1.77
• Example 3 1.578
• 32 132 80 >535 1.69
• Comparative 1.583 30 145 8 >535 1.34
• Example 1 Comparative 1.527 57 80 95 16 1.55
• Example 2 Comparative — — 117 — — — Example 3 Comparative — — 117 — — — Example 4 Comparative 1.564 36 108 66 10 3.15
• Example 5 Comparative 1.561 36 118 68 150 2.83
• Example 6 Comparative 1.564

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• 2010
  • 2010-08-11 KR KR1020127006201A patent/KR101777884B1/ko active IP Right Grant
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